The present invention relates to a liquid detergent.
The liquid detergent used in an ordinary home may include a detergent for a hard surface, which is directed to a metal, a glass, a ceramic, a plastic and the like, and a detergent for a clothing, which can be applied directly to smears in or on a clothing. These detergents are blended with solvents such as, for example, methyl cellosolve and methyl carbitol in order to improve their detergent effect. However, the liquid detergent blended with these solvents are still not satisfactory in respect of detergency for persistent sebum smears such as smears in or on collars and cuffs and denatured-oil smears etc. in kitchens as well as smells derived from the solvents.
Meanwhile, JP-A 7-500861 describes a detergent composition comprising a mixture of an alkyl monoglyceryl ether and an alkyl diglyceryl ether as nonionic surfactants and a anionic surfactant. Further, U.S. Pat. No. 4,430,237 describes a detergent composition comprising a mixture of an alkyl glyceryl ether, an alkyl diglyceryl ether and an alkyl triglyceryl ether as nonionic surfactants. However, these compositions are still not satisfactory in respect of detergency for sebum smears etc. because of higher contents of the diglyceryl and triglyceryl ethers relative to the monoglyceryl ether.
In addition, a detergent for human body having improvement of its foaming property and rinsing property is demanded in particular for hair shampoo, body shampoo, face washing, hand washing and so on.
The object of the present invention is to provide a liquid detergent being excellent in detergency for persistent sebum smears such as smears in or on collars and cuffs and for denatured-oil smears etc. in kitchens and further having good smell as detergent.
The present invention relates to a liquid-detergent comprising (a) a compound represented by the following formula (1), (b) a compound represented by the following formula (2), (c) a compound represented by the following formula (3) and (d) a surfactant, wherein (a)+(b)+(c)=0.1 to 50% by weight, (a)/[(a)+(b)+(c)]=0.5 to 0.99, (b)/[(a)+(b)+(c)]=0.005 to 0.25 and (c)/[(a)+(b)+(c)]=0.005 to 0.25 (of which each and all are the ratios by weight): 
wherein R is a hydrocarbon group containing from 1 up to 16 carbon atoms, X is selected from the group consisting of a hydroxyl group and an OR group, Y is also selected from the group consisting of a hydroxyl group and an OR group, and Z is selected from the group consisting of a hydroxyl group, 
and W is also selected from the group consisting of a hydroxyl group, 
provided that either Z or W is a hydroxyl group.
The above defined composition comprises three different glyceryl ether compounds from one another, (1), (2) and (3). It is preferable that both of Z and W are not hydroxyl group.
A composition containing the above-shown liquid detergent is useful as a detergent for domestic use such as washing of cloth, woven or non-woven fabrics, textile goods, tableware, dishes, glass, cup, metal goods, ceramic goods, plastic goods, kitchen, bathroom, bathtub, furniture and human body.
(a) to (c) Glyceryl Ether Type Compounds
The compounds represented by the following formulae (1), (2) and (3) can be used as the components (a), (b) and (c) in the present invention: 
wherein R represents a hydrocarbon group having 1 to 16 carbon atoms, X is selected from the group consisting of a hydroxyl group and an OR group, Y is also selected from the group consisting of a hydroxyl group and an OR group, Z is selected from the group consisting of a hydroxyl group, 
and W is also selected from the group consisting of a hydroxyl group, 
provided that either Z or W is a hydroxyl group. Here, it is preferable that both of Z and W are not hydroxyl group. Further, at least one of Z and W is preferably a hydroxyl group.
In the formulae, R is preferably a hydrocarbon group having 3 to 12 carbon atoms, particularly 4 to 10 carbon atoms, in respect of improving the detergency. In particular, when the liquid detergent is used in washing by application, R is preferably an alkyl group having 7 to 9 carbon atoms, particularly 8 carbon atoms, in respect of detergent performance towards sebum smears in or on collars, cuffs etc. Further, when it is used as a detergent for hard surfaces, R is preferably an alkyl group having 4 to 6 carbon atoms. X, Y and Z are preferably hydroxyl groups. In addition, W is preferably 
Specifically, the following compounds (4) to (9) can be mentioned as each of the above-described compounds: 
wherein R represents an alkyl group having 1 to 16 carbon atoms, preferably an alkyl group having 4 to 6 or 8 carbon atoms.
Among them, the compounds (4), (5), (6) and (7) are preferable, and the compounds (4) and (5) are preferable in respect of detergent performance in washing by application in particular.
In respect of detergency and smell, the total amount ((a)+(b)+(c)) of the components (a), (b) and (c) in the present invention is 0.1 to 50% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, as compared with the liquid detergent.
The ratio by weight of the component (a) to the said total amount ((a)/[(a)+(b)+(c)]) is 0.5 to 0.99, preferably 0.8 to 0.99, more preferably 0.86 to 0.99 and particularly preferably 0.9 to 0.99. Then, the ratio by weight of the component (b) to the said total amount ((b)/[(a)+(b)+(c)]) is 0.005 to 0.25, preferably 0.005 to 0.1, more preferably 0.005 to 0.07 and particularly preferably 0.005 to 0.05. Further, the ratio of the component (c) to the said total amount ((c)/[(a)+(b)+(c)]) is 0.005 to 0.25, preferably 0.005 to 0.1, more preferably 0.005 to 0.07 and particularly preferably 0.005 to 0.05.
The ratio by weight of the component (b) to the component (a) is preferably 0.001 to 0.1, more preferably 0.005 to 0.05, and the ratio by weight of the component (c) to the component (a) is preferably 0.001 to 0.15, more preferably 0.005 to 0.1. Further, in respect of improving the detergency, the ratio of the total amount of the components (b) and (c) to the component (a) (that is, [(b)+(c)]/(a)) is preferably 0.001 to 0.3, more preferably 0.005 to 0.2 and particularly preferably 0.01 to 0.15.
By the way, it is general that the compounds represented by the formulae (1) to (3) are produced by a process of reacting an epoxy compound such as, for example, epihalohydrin and glycidol using an acid catalyst such as BF3. However, the reaction of an alcohol with the epoxy compound occurs at random at 1- and 2-positions of the epoxy compound so that multiple addition-products are also formed. Accordingly, the resultant product is a mixture of the compound having an alcohol added at 1-position and being represented by the formula (1), the compound having an alcohol added at 2-position and being represented by the formula (2) and the multimer (which may be a multimeric compound, an oligomer or a polymer) having a large number of glyceryl groups added and being represented by the formula (3), and therefore the composition comprising the compounds (a) to (c) in a specific ratio for blend in the present invention was hardly obtained technically and economically.
Under these circumstances, the applicant found a method of using, for instance, an aluminum catalyst represented by the formula (10) described in WO 98/50389 as a method of economically and efficiently producing the above-described compounds in the present invention:
Al(OSO2xe2x80x94R1)1(OR2)m(OR3)nxe2x80x83xe2x80x83(10)
wherein R1 represents a hydrocarbon group which may have a substitutent-group, R2 is selected from the group consisting of a hydrocarbon group and a substituent hydrocarbon group, R3 is selected from the group consisting of a hydrocarbon group and a substituted hydrocarbon group, l is 1 to 3, and each of m and n is an integer of 0 to 2, provided that l+m+n=3.
Here, R1 is preferably an alkyl group having 1 to 5 carbon atoms (preferably a methyl group) or an aryl group which may have a hydroxyl group or an alkyl group having 1 to 5 carbon atoms (preferably a 4-tolyl (4-methylbenzoyl) group or a 4-hydroxyphenyl group). R2 or R3 is preferably an alkyl group having 1 to 10 carbon atoms (e.g. an isopropyl group or an octyl group) and a phenyl group.
The catalyst mentioned above can be produced by reacting e.g. sulfonic acid or the like with trialkyl aluminum, trialkoxy aluminum, trihalogenated aluminum or the like to substitute a part or all of alkyl groups, alkoxyl groups and halogen groups of the said aluminum compounds by the said sulfonate and then substituting the remaining alkyl groups, alkoxyl groups or halogen groups by a suitable alcohol or phenol. Such a substitution reaction as this is carried out by mixing them under heating in a solvent such as hydrocarbon and alcohol.
When the above-described aluminum catalyst is used in the present invention, it is good that an epoxy compound such as epihalohydrin and glycidol is used in an amount of 0.5 to 1.5 equivalents by mole, preferably 1.0 to 1.2 equivalents by mole, as compared with an alcohol having 1 to 16 carbon atoms, and the aluminum catalyst represented by the formula (10) is used in an amount of 0.001 to 0.1 equivalent by mole, preferably 0.01 to 0.05 equivalent by mole, as compared with the said alcohol, and the reaction is carried out at a reaction temperature of 10 to 120xc2x0 C., preferably 70 to 110xc2x0 C., for 1 to 5 hours. By use of the above-described method, the compounds (a) to (c) can be easily prepared in the desired ratio for blend.
(d) Surfactant
One or more members of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be mentioned as the surfactant (d) in the present invention. In particular, the anionic surfactant and/or nonionic surfactant is preferable. The anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, fatty acid salts, alkyl or alkenyl ether carboxylates, xcex1-sulfonic acid salts or esters thereof; the nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, alkyl polyglucosides, glucose amides and the like; the cationic surfactants include quaternary ammonium salts and the like; and the amphoteric surfactants include amine oxides, sulfobetaine, carbobetaine and the like.
In particular, the following surfactants (i) to (iv) are preferable in respect of detergency.
(i) A linear alkyl benzene sulfonate which has an alkyl group having 10 to 14 carbon atoms.
(ii) A polyoxyethylene alkyl or alkenyl ether sulfate which has an alkyl or alkenyl group having 8 to 18 carbon atoms, which preferably has an alkyl or alkenyl group having 10 to 16 carbon atoms and being an adduct with 1 to 8 moles, preferably 1 to 6 moles, of EO on the average.
(iii) A polyoxyalkylene type nonionic surfactant represented by the formula (11):
R4Xxe2x80x94[(PO)m(EO)nxe2x80x94H]pxe2x80x83xe2x80x83(11)
wherein R4 represents a hydrocarbon group having 8 to 20 preferably 10 to 18, carbon atoms; X represents an oxygen atom or a nitrogen atom; PO represents propylene oxide; EO represents ethylene oxide. Here, although the order for adding EO and PO is not minded, the form of addition is a random addition product or block addition product (, a block addition product is preferable in particular). Then, each of m and n is independently an integer of 0 to 20, and moreover n+m=3 to 25, preferably 5 to 20. Further, when X is an oxygen atom, p=1 and when X is a nitrogen atom, p=2.
(iv) An alkyl polyglucoside which has an alkyl group having 8 to 16 carbon atoms, which preferably has an alkyl group having 8 to 14 carbon atoms, wherein the average degree of polymerization of glucose is 1 to 3, preferably 1 to 2.
If the polyoxyalkylene type nonionic surfactant (iii) described above is blended, it is preferable to use a matter satisfying at least one of the following requirements (I) to (III).
(I) Among the compounds represented by the above-mentioned formula (11), the polyoxyalkylene alkyl ether type nonionic surfactant wherein R4 is an alkyl group derived from a secondary alcohol and X is an oxygen atom.
(II) Among the compounds represented by the above-mentioned formula (11), the polyoxyethylene polyoxypropylene alkyl ether type nonionic surfactant wherein m and n means the average number of added moles, m is 4 to 16 and n is 1 to 5, and X is an oxygen atom.
(III) Among the compounds represented by the above-mentioned formula (11), the polyoxyethylene alkyl ether type nonionic surfactant wherein m is 0 and n is 5 to 15 in terms of the average number of moles, which has the compound of n=0 in a blended amount of 5% by weight or less, wherein when the number of added moles of the compound in the amount of maximum % by weight is made to n(max), the total of compounds having their numbers of added moles from [n(max)xe2x88x922] to [n (max)+2] is 55% by weight or more, and wherein X is an oxygen atom.
When the compound (I) is blended as component (d), the liquid detergent is excellent in dispersibility and stability at storage. In particular, the liquid detergent comprising the compounds (I) to (III) as component (d) exhibits excellent detergency towards sebum smears by using it for clothing.
In the present invention, the content of component (d) in the liquid detergent is 0.1 to 50% by weight, and the ratio by weight of the component (d) to the total amount of the components (a), (b) and (c) (that is, (d)/[(a)+(b)+(c)]) in the liquid detergent of the present invention is preferably 0.1 to 10, more preferably 1.2 to 10, most preferably 1.5 to 5, in respect of improving the detergent performance. When the liquid detergent is used for clothing, the content of component (d) is preferably 30 to 50% by weight, when it is used for directly spraying or applying onto hard surfaces, the content thereof is preferably 0.1 to 10% by weight, and when it is used for the liquid detergent for tableware or human body, the content thereof is 8 to 50% by weight.
Various components such as alkalizing agents, chelating agents, viscosity regulators and hydrotropic agents can be blended into the liquid detergent of the present invention as far as the performance or effect of the present invention is not deteriorated.
The alkali agents include hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, carbonates such as sodium carbonate, potassium carbonate and sodium sesquicarbonate (sodium monohydrogen-dicarbonate), silicates such as sodium silicate and potassium silicate, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol, as well as morpholine and ammonia. Sodium hydroxide, potassium hydroxide, monoethanolamine, 2-amino-2-methyl-1-propanol, morpholine or ammonia is particularly preferable in respect of improving the detergency. The content of the alkali agent in the liquid detergent is preferably 0 to 20% by weight, more preferably 0.1 to 20% by weight.
The chelating agents include (i) phosphorus (or phosphoric) acid type compounds such as phytic acid or salts thereof, (ii) phosphonic acids such as ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid or salts thereof, (iii) phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and xcex1-methylphosphonosuccinic acid or salts thereof, (iv) amino acids such as aspartic acid, glutamic acid and glycine or salts thereof, (v) aminopolyacetic acids such as nitrilotriacetic acid, iminodiacetic acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, glycol ether diamine tetraacetic acid, hydroxy ethyl iminodiacetic acid, triethylene tetraamine hexaacetic acid and djenkolic acid or salts thereof, (vi) organic acids such as diglycollic acid, oxydisuccinic acid, carboxy methyl oxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, carboxy methyl succinic acid and carboxy methyl tartaric acid or salts thereof, (vii) aminopoly(methylene phosphonic acid) polyethylene polyamine poly(methylene phosphonic acid), or salts thereof, (viii) alkyl glycine-N,N-diacetic acid, aspartic acid-N,N-diacetic acid, serine-N,N-diacetic acid, N,N-dicarboxymethyl glutamic acid (or glutamic acid diacetic acid), ethylene diamine disuccinic acid or salts thereof, and (ix) condensed phosphates such as pyrophosphate. Among them, the above-described compound (ii), (v), (vi) or (viii), particularly (ii), (v) or (viii), is preferable. The content of the chelating agent in the liquid detergent is preferably 0 to 30% by weight, more preferably 0.01 to 15% by weight in respect of improving the detergency.
The hydrotropic agents include salts of organic acids such as p-toluenesulfonic acid, m-xylenesulfonic acid, citric acid, malic acid and succinic acid (salts of alkaline metal are preferable). The content of the hydrotropic agent in the liquid detergent is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight.
As other components, it is possible to use lower alcohols such as ethanol and isopropanol, polyhydric alcohols (or polyol) such as glycerol and sorbitol, chlorides such as sodium chloride, potassium chloride and calcium chloride, sulfates such as sodium sulfate, potassium sulfate and calcium sulfate, sulfites such as sodium sulfite and potassium sulfite, enzymes such as cellulase, amylase, pectinase, protease and lipase, as well as perfumes, pigments (or dyes), preservatives, fungicides (or anti-fungus agents), thickeners and the like. In particular, when the product of the present invention is used as detergent for human body, the product may contain a moisturizer, a conditioning agent, a vitamin compound, a plant- or vegetable-extract, anti-inflammatory agent, anti-dandruff agent, an absorbent of ultraviolet ray or the like.
For use of the liquid detergent of the present invention, e.g. the above-described components (a) to (d) and optional components are diluted preferably with water. In particular, water, from which hardness components, heavy metals etc. have been removed, such as deionized water, is desirable. The content of the water in the liquid detergent is preferably 40 to 99% by weight, more preferably 50 to 95% by weight.
The liquid detergent of the present invention is excellent in detergency for persistent sebum smears such as smears in or on collars and cuffs and for denatured-oil smears etc. in kitchens and also excellent in handling without smells derived from the solvent components. In particular, the liquid detergent exhibits excellent detergent performance, when it is used in washing by application.